Legacy of anthropogenic lead in urban soils: Co-occurrence with metal(loids) and fallout radionuclides, isotopic fingerprinting, and in vitro bioaccessibility.

Anthropogenic lead (Pb) in soils poses risks to human health, particularly to the neuropsychological development of exposed children. Delineating the sources and potential bioavailability of soil Pb, as well as its relationship with other contaminants is critical in mitigating potential human exposure. Here, we present an integrative geochemical analysis of total elemental concentrations, radionuclides of 137Cs and 210Pb, Pb isotopic compositions, and in vitro bioaccessibility of Pb in surface soils sampled from different locations near Durham, North Carolina. Elevated Pb (>400 mg/kg) was commonly observed in soils from urban areas (i.e., near residential house foundation and along urban streets), which co-occurred with other potentially toxic metal(loids) such as Zn, Cd, and Sb. In contrast, soils from city parks and suburban areas had systematically lower concentrations of metal(loids) that were comparable to geological background. The activities of 137Cs and excess 210Pb, coupled with their correlations with Pb and co-occurring metal(loids) were used to indicate the persistence and remobilization of historical atmospherically deposited contaminants. Coupled with total Pb concentrations, the soil Pb isotopic compositions further indicated that house foundation soils had significant input of legacy lead-based paint (mean = 1.1895 and 2.0618 for 206Pb/207Pb and 208Pb/206Pb, respectively), whereas urban streetside soils exhibited a clear mixed origin, dominantly of legacy leaded gasoline (1.2034 and 2.0416) and atmospheric deposition (1.2004-1.2055 and 2.0484-2.0525). The in vitro bioaccessibility of Pb in contaminated urban soils furthermore revealed that more than half of Pb in the contaminated soils was potentially bioavailable, whose Pb isotope ratios were identical to that of bulk soils, demonstrating the utility of using Pb isotopes for tracking human exposure to anthropogenic Pb in soils and house dust. Overall, this study demonstrated a holistic assessment for comprehensively understanding anthropogenic Pb in urban soils, including its co-occurrence with other toxic contaminants, dominant sources, and potential bioavailability upon human exposure.

A critical review on the occurrence and distribution of the uranium- and thorium-decay nuclides and their effect on the quality of groundwater.

This critical review presents the key factors that control the occurrence of natural elements from the uranium- and thorium-decay series, also known as naturally occurring radioactive materials (NORM), including uranium, radium, radon, lead, polonium, and their isotopes in groundwater resources. Given their toxicity and radiation, elevated levels of these nuclides in drinking water pose human health risks, and therefore understanding the occurrence, sources, and factors that control the mobilization of these nuclides from aquifer rocks is critical for better groundwater management and human health protection. The concentrations of these nuclides in groundwater are a function of the groundwater residence time relative to the decay rates of the nuclides, as well as the net balance between nuclides mobilization (dissolution, desorption, recoil) and retention (adsorption, precipitation). This paper explores the factors that control this balance, including the relationships between the elemental chemistry (e.g., solubility and speciation), lithological and hydrogeological factors, groundwater geochemistry (e.g., redox state, pH, ionic strength, ion-pairs availability), and their combined effects and interactions. The various chemical properties of each of the nuclides results in different likelihoods for co-occurrence. For example, the primordial 238U, 222Rn, and, in cases of high colloid concentrations also 210Po, are all more likely to be found in oxic groundwater. In contrast, in reducing aquifers, Ra nuclides, 210Pb, and in absence of high colloid concentrations, 210Po, are more mobile and frequently occur in groundwater. In highly permeable sandstone aquifers that lack sufficient adsorption sites, Ra is often enriched, even in low salinity and oxic groundwater. This paper also highlights the isotope distributions, including those of relatively long-lived nuclides (238U/235U) with abundances that depend on geochemical conditions (e.g., fractionation induced from redox processes), as well as shorter-lived nuclides (234U/238U, 228Ra/226Ra, 224Ra/228Ra, 210Pb/222Rn, 210Po/210Pb) that are strongly influenced by physical (recoil), lithological, and geochemical factors. Special attention is paid in evaluating the ability to use these isotope variations to elucidate the sources of these nuclides in groundwater, mechanisms of their mobilization from the rock matrix (e.g., recoil, ion-exchange), and retention into secondary mineral phases and ion-exchange sites.

The impact of using low-saline oilfield produced water for irrigation on water and soil quality in California.

The consecutive occurrence of drought and reduction in natural water availability over the past several decades requires searching for alternative water sources for the agriculture sector in California. One alternative source to supplement natural waters is oilfield produced water (OPW) generated from oilfields adjacent to agricultural areas. For over 25 years, OPW has been blended with surface water and used for irrigation in the Cawelo Water District of Kern County, as permitted by California Water Board policy. This study aims to evaluate the potential environmental impact, soil quality, and crop health risks of this policy. We examined a large spectrum of salts, metals, radionuclides (226Ra and 228Ra), and dissolved organic carbon (DOC) in OPW, blended OPW used for irrigation, groundwater, and soils irrigated by the three different water sources. We found that all studied water quality parameters in the blended OPW were below current California irrigation quality guidelines. Yet, soils irrigated by blended OPW showed higher salts and boron relative to soils irrigated by groundwater, implying long-term salts and boron accumulation. We did not, however, find systematic differences in 226Ra and 228Ra activities and DOC in soils irrigated by blended or unblended OPW relative to groundwater-irrigated soils. Based on a comparison of measured parameters, we conclude that the blended low-saline OPW used in the Cawelo Water District of California is of comparable quality to the local groundwater in the region. Nonetheless, the salt and boron soil accumulation can pose long-term risks to soil sodification, groundwater salinization, and plant health; as such, the use of low-saline OPW for irrigation use in California will require continual blending with fresh water and planting of boron-tolerant crops to avoid boron toxicity.

Factors Controlling the Risks of Co-occurrence of the Redox-Sensitive Elements of Arsenic, Chromium, Vanadium, and Uranium in Groundwater from the Eastern United States.

The co-occurrence of contaminants in drinking water may pose enhanced risks to health beyond the effects of single contaminants. Here, we investigated the co-occurrence of four health-relevant redox-sensitive elements (U, As, V, and Cr) in 1494 groundwater wells across North Carolina. The highest concentrations of these elements were measured mostly in groundwater from fractured igneous and metamorphic formations throughout the Piedmont region. Arsenic occurred most frequently in suboxic to mixed redox character groundwater, whereas U, V, and Cr occurred mostly in oxic groundwater. Occurrences of As, and to a lesser extent U, increased with pH, likely reflecting desorption, while higher Cr and V levels were measured in near-neutral pH and oxic groundwater, reflecting greater sensitivity to redox conditions. Due to similar geochemistry, V and Cr co-occurred most frequently. Concentrations of V and Cr(VI) co-exceeded health recommendations from the NC Department of Health and Human Services in up to 84% of wells from the King's Mountain Belt and the Charlotte and Milton Belts of the Piedmont region. This study highlights the large gap between health recommendations and enforceable regulations and demonstrates a degree of co-occurrence between redox-sensitive elements, which may pose additional risks to groundwater-reliant individuals.

Origin of Flowback and Produced Waters from Sichuan Basin, China.

Shale gas extraction through hydraulic fracturing and horizontal drilling is increasing in China, particularly in Sichuan Basin. Production of unconventional shale gas with minimal environmental effects requires adequate management of wastewater from flowback and produced water (FP water) that is coextracted with natural gas. Here we present, for the first time, inorganic chemistry and multiple isotope (oxygen, hydrogen, boron, strontium, radium) data for FP water from 13 shale gas wells from the Lower Silurian Longmaxi Formation in the Weiyuan gas field, as well as produced waters from 35 conventional gas wells from underlying (Sinian, Cambrian) and overlying (Permian, Triassic) formations in Sichuan Basin. The chemical and isotope data indicate that the formation waters in Sichuan Basin originated from relics of different stages of evaporated seawater modified by water-rock interactions. The FP water from shale gas wells derives from blending of injected hydraulic fracturing water and entrapped saline (Cl ∼ 50,000 mg/L) formation water. Variations in the chemistry, δ18O, δ11B, and 87Sr/86Sr of FP water over time indicate that the mixing between the two sources varies with time, with a contribution of 75% (first 6 months) to 20% (>year) of the injected hydraulic fracturing water in the blend that compose the FP water. Mass-balance calculation suggests that the returned hydraulic fracturing water consisted of 28-49% of the volume of the injected hydraulic fracturing water, about a year after the initial hydraulic fracturing. We show differential mobilization of Na, B, Sr, and Li from the shale rocks during early stages of operation, which resulted in higher Na/Cl, B/Cl, Li/Cl, and 87Sr/86Sr and lower δ11B of the FP water during early stages of FP water formation relative to the original saline formation water recorded in late stages FP water. This study provides a geochemical framework for characterization of formation waters from different geological strata, and thus the ability to distinguish between different sources of oil and gas wastewater in Sichuan Basin.

Pre-drill Groundwater Geochemistry in the Karoo Basin, South Africa.

Enhanced production of unconventional hydrocarbons in the United States has driven interest in natural gas development globally, but simultaneously raised concerns regarding water quantity and quality impacts associated with hydrocarbon extraction. We conducted a pre-development assessment of groundwater geochemistry in the critically water-restricted Karoo Basin, South Africa. Twenty-two springs and groundwater samples were analyzed for major dissolved ions, trace elements, water stable isotopes, strontium and boron isotopes, hydrocarbons and helium composition. The data revealed three end-members: a deep, saline groundwater with a sodium-chloride composition, an old, deep freshwater with a sodium-bicarbonate-chloride composition and a shallow, calcium-bicarbonate freshwater. In a few cases, we identified direct mixing of the deep saline water and shallow groundwater. Stable water isotopes indicate that the shallow groundwater was controlled by evaporation in arid conditions, while the saline waters were diluted by apparently fossil meteoric water originated under wetter climatic conditions. These geochemical and isotopic data, in combination with elevated helium levels, suggest that exogenous fluids are the source of the saline groundwater and originated from remnant seawater prior to dilution by old meteoric water combined with further modification by water-rock interactions. Samples with elevated methane concentrations (>14 ccSTP/kg) were strongly associated with the sodium-chloride water located near dolerite intrusions, which likely provide a preferential pathway for vertical migration of deeply sourced hydrocarbon-rich saline waters to the surface. This pre-drill evaluation indicates that the natural migration of methane- and salt-rich waters provides a source of geogenic contamination to shallow aquifers prior to shale gas development in the Karoo Basin.

Global biogeochemical cycle of vanadium.

Synthesizing published data, we provide a quantitative summary of the global biogeochemical cycle of vanadium (V), including both human-derived and natural fluxes. Through mining of V ores (130 × 109 g V/y) and extraction and combustion of fossil fuels (600 × 109 g V/y), humans are the predominant force in the geochemical cycle of V at Earth's surface. Human emissions of V to the atmosphere are now likely to exceed background emissions by as much as a factor of 1.7, and, presumably, we have altered the deposition of V from the atmosphere by a similar amount. Excessive V in air and water has potential, but poorly documented, consequences for human health. Much of the atmospheric flux probably derives from emissions from the combustion of fossil fuels, but the magnitude of this flux depends on the type of fuel, with relatively low emissions from coal and higher contributions from heavy crude oils, tar sands bitumen, and petroleum coke. Increasing interest in petroleum derived from unconventional deposits is likely to lead to greater emissions of V to the atmosphere in the near future. Our analysis further suggests that the flux of V in rivers has been incremented by about 15% from human activities. Overall, the budget of dissolved V in the oceans is remarkably well balanced-with about 40 × 109 g V/y to 50 × 109 g V/y inputs and outputs, and a mean residence time for dissolved V in seawater of about 130,000 y with respect to inputs from rivers.

Naturally Occurring Radioactive Materials in Uranium-Rich Coals and Associated Coal Combustion Residues from China.

Most coals in China have uranium concentrations up to 3 ppm, yet several coal deposits are known to be enriched in uranium. Naturally occurring radioactive materials (NORM) in these U-rich coals and associated coal combustion residues (CCRs) have not been well characterized. Here we measure NORM (Th, U, 228Ra, 226Ra, and 210Pb) in coals from eight U-rich coal deposits in China and the associated CCRs from one of these deposits. We compared NORM in these U-rich coals and associated CCRs to CCRs collected from the Beijing area and natural loess sediments from northeastern China. We found elevated U concentrations (up to 476 ppm) that correspond to low 232Th/238U and 228Ra/226Ra activity ratios (≪1) in the coal samples. 226Ra and 228Ra activities correlate with 238U and 232Th activities, respectively, and 226Ra activities correlate well with 210Pb activities across all coal samples. We used measured NORM activities and ash yields in coals to model the activities of CCRs from all U-rich coals analyzed in this study. The activities of measured and modeled CCRs derived from U-rich coals exceed the standards for radiation in building materials, particularly for CCRs originating from coals with U > 10 ppm. Since beneficial use of high-U Chinese CCRs in building materials is not a suitable option, careful consideration needs to be taken to limit potential air and water contamination upon disposal of U- and Ra-rich CCRs.

Maternal blood cadmium, lead and arsenic levels, nutrient combinations, and offspring birthweight.

BACKGROUND: Cadmium (Cd), lead (Pb) and arsenic (As) are common environmental contaminants that have been associated with lower birthweight. Although some essential metals may mitigate exposure, data are inconsistent. This study sought to evaluate the relationship between toxic metals, nutrient combinations and birthweight among 275 mother-child pairs. METHODS: Non-essential metals, Cd, Pb, As, and essential metals, iron (Fe), zinc (Zn), selenium (Se), copper (Cu), calcium (Ca), magnesium (Mg), and manganese (Mn) were measured in maternal whole blood obtained during the first trimester using inductively coupled plasma mass spectrometry. Folate concentrations were measured by microbial assay. Birthweight was obtained from medical records. We used quantile regression to evaluate the association between toxic metals and nutrients due to their underlying wedge-shaped relationship. Ordinary linear regression was used to evaluate associations between birth weight and toxic metals. RESULTS: After multivariate adjustment, the negative association between Pb or Cd and a combination of Fe, Se, Ca and folate was robust, persistent and dose-dependent (p < 0.05). However, a combination of Zn, Cu, Mn and Mg was positively associated with Pb and Cd levels. While prenatal blood Cd and Pb were also associated with lower birthweight. Fe, Se, Ca and folate did not modify these associations. CONCLUSION: Small sample size and cross-sectional design notwithstanding, the robust and persistent negative associations between some, but not all, nutrient combinations with these ubiquitous environmental contaminants suggest that only some recommended nutrient combinations may mitigate toxic metal exposure in chronically exposed populations. Larger longitudinal studies are required to confirm these findings.

Water Availability for Shale Gas Development in Sichuan Basin, China.

Unconventional shale gas development holds promise for reducing the predominant consumption of coal and increasing the utilization of natural gas in China. While China possesses some of the most abundant technically recoverable shale gas resources in the world, water availability could still be a limiting factor for hydraulic fracturing operations, in addition to geological, infrastructural, and technological barriers. Here, we project the baseline water availability for the next 15 years in Sichuan Basin, one of the most promising shale gas basins in China. Our projection shows that continued water demand for the domestic sector in Sichuan Basin could result in high to extremely high water stress in certain areas. By simulating shale gas development and using information from current water use for hydraulic fracturing in Sichuan Basin (20,000-30,000 m(3) per well), we project that during the next decade water use for shale gas development could reach 20-30 million m(3)/year, when shale gas well development is projected to be most active. While this volume is negligible relative to the projected overall domestic water use of ∼36 billion m(3)/year, we posit that intensification of hydraulic fracturing and water use might compete with other water utilization in local water-stress areas in Sichuan Basin.

Iodide, bromide, and ammonium in hydraulic fracturing and oil and gas wastewaters: environmental implications.

The expansion of unconventional shale gas and hydraulic fracturing has increased the volume of the oil and gas wastewater (OGW) generated in the U.S. Here we demonstrate that OGW from Marcellus and Fayetteville hydraulic fracturing flowback fluids and Appalachian conventional produced waters is characterized by high chloride, bromide, iodide (up to 56 mg/L), and ammonium (up to 420 mg/L). Br/Cl ratios were consistent for all Appalachian brines, which reflect an origin from a common parent brine, while the I/Cl and NH4/Cl ratios varied among brines from different geological formations, reflecting geogenic processes. There were no differences in halides and ammonium concentrations between OGW originating from hydraulic fracturing and conventional oil and gas operations. Analysis of discharged effluents from three brine treatment sites in Pennsylvania and a spill site in West Virginia show elevated levels of halides (iodide up to 28 mg/L) and ammonium (12 to 106 mg/L) that mimic the composition of OGW and mix conservatively in downstream surface waters. Bromide, iodide, and ammonium in surface waters can impact stream ecosystems and promote the formation of toxic brominated-, iodinated-, and nitrogen disinfection byproducts during chlorination at downstream drinking water treatment plants. Our findings indicate that discharge and accidental spills of OGW to waterways pose risks to both human health and the environment.

Selenium speciation in coal ash spilled at the Tennessee Valley Authority Kingston site.

Selenium (Se) in coal ash spills poses a threat to adjacent ecosystems because of its potential to mobilize and bioaccumulate in aquatic organisms. Given that the mobility and bioavailability of Se is controlled by its valence states, we aimed to define Se speciation in coal ash solids and examine the relationships between Se speciation and the magnitude of its mobilization from coal ash. We used coal ash samples from the Tennessee Valley Authority (TVA)-Kingston fossil plant and the site of a coal ash spill that occurred in 2008 in Tennessee. Results of X-ray absorption spectroscopic analyses showed that Se in coal ash samples was a mixture of elemental Se(0) and Se oxyanions. The amount of leachable Se increased with an increase of pH from 3 to 13. At the natural pH of coal ash samples (from pH 7.6 to 9.5), the leachable Se was comprised of Se oxyanions, mainly selenite. This was observed by both direct quantification of Se oxyanions in the leachate and the corresponding loss of Se oxyanions in the solid phase. At pH 12, however, the Se release appeared to derive from both desorption of Se oxyanions and oxidative dissolution of elemental Se(0). Our results indicate that Se oxyanions are the most labile species; however, the magnitude of Se mobilization will increase if the waste material is subjected to alkaline conditions.

Isotopic imprints of mountaintop mining contaminants.

Mountaintop mining (MTM) is the primary procedure for surface coal exploration within the central Appalachian region of the eastern United States, and it is known to contaminate streams in local watersheds. In this study, we measured the chemical and isotopic compositions of water samples from MTM-impacted tributaries and streams in the Mud River watershed in West Virginia. We systematically document the isotopic compositions of three major constituents: sulfur isotopes in sulfate (δ(34)SSO4), carbon isotopes in dissolved inorganic carbon (δ(13)CDIC), and strontium isotopes ((87)Sr/(86)Sr). The data show that δ(34)SSO4, δ(13)CDIC, Sr/Ca, and (87)Sr/(86)Sr measured in saline- and selenium-rich MTM impacted tributaries are distinguishable from those of the surface water upstream of mining impacts. These tracers can therefore be used to delineate and quantify the impact of MTM in watersheds. High Sr/Ca and low (87)Sr/(86)Sr characterize tributaries that originated from active MTM areas, while tributaries from reclaimed MTM areas had low Sr/Ca and high (87)Sr/(86)Sr. Leaching experiments of rocks from the watershed show that pyrite oxidation and carbonate dissolution control the solute chemistry with distinct (87)Sr/(86)Sr ratios characterizing different rock sources. We propose that MTM operations that access the deeper Kanawha Formation generate residual mined rocks in valley fills from which effluents with distinctive (87)Sr/(86)Sr and Sr/Ca imprints affect the quality of the Appalachian watersheds.

Groundwater quality and its health impact: An assessment of dental fluorosis in rural inhabitants of the Main Ethiopian Rift.

This study aims to assess the link between fluoride content in groundwater and its impact on dental health in rural communities of the Ethiopian Rift. A total of 148 water samples were collected from two drainage basins within the Main Ethiopian Rift (MER). In the Ziway-Shala basin in particular, wells had high fluoride levels (mean: 9.4±10.5mg/L; range: 1.1 to 68 mg/L), with 48 of 50 exceeding the WHO drinking water guideline limit of 1.5mg/L. Total average daily intake of fluoride from drinking groundwater (calculated per weight unit) was also found to be six times higher than the No-Observed-Adverse-Effects-Level (NOAEL) value of 0.06 mg/kg/day. The highest fluoride levels were found in highly-alkaline (pH of 7 to 8.9) groundwater characterized by high salinity; high concentrations of sodium (Na⁺), bicarbonate (HCO3⁻), and silica (SiO2); and low concentrations of calcium (Ca²âº). A progressive Ca²âº decrease along the groundwater flow path is associated with an increase of fluoride in the groundwater. The groundwater quality problem is also coupled with the presence of other toxic elements, such as arsenic (As) and uranium (U). The health impact of fluoride was evaluated based on clinical examination of dental fluorosis (DF) among local residents using the Thylstrup and Fejerskov index (TFI). In total, 200 rural inhabitants between the ages of 7 and 40 years old using water from 12 wells of fluoride range of 7.8-18 mg/L were examined. Signs of DF (TF score of ≥ 1) were observed in all individuals. Most of the teeth (52%) recorded TF scores of 5 and 6, followed by TF scores of 3 and 4 (30%), and 8.4% had TF scores of 7 or higher. Sixty percent of the teeth exhibited loss of the outermost enamel. Within the range of fluoride contents, we did not find any correlation between fluoride content and DF. Finally, preliminary data suggest that milk intake has contributed to reducing the severity of DF. The study highlights the apparent positive role of milk on DF, and emphasizes the importance of nutrition in management efforts to mitigate DF in the MER and other parts of the world.

Cumulative impacts of mountaintop mining on an Appalachian watershed.

Mountaintop mining is the dominant form of coal mining and the largest driver of land cover change in the central Appalachians. The waste rock from these surface mines is disposed of in the adjacent river valleys, leading to a burial of headwater streams and dramatic increases in salinity and trace metal concentrations immediately downstream. In this synoptic study we document the cumulative impact of more than 100 mining discharge outlets and approximately 28 km(2) of active and reclaimed surface coal mines on the Upper Mud River of West Virginia. We measured the concentrations of major and trace elements within the tributaries and the mainstem and found that upstream of the mines water quality was equivalent to state reference sites. However, as eight separate mining-impacted tributaries contributed their flow, conductivity and the concentrations of selenium, sulfate, magnesium, and other inorganic solutes increased at a rate directly proportional to the upstream areal extent of mining. We found strong linear correlations between the concentrations of these contaminants in the river and the proportion of the contributing watershed in surface mines. All tributaries draining mountaintop-mining-impacted catchments were characterized by high conductivity and increased sulfate concentration, while concentrations of some solutes such as Se, Sr, and N were lower in the two tributaries draining reclaimed mines. Our results demonstrate the cumulative impact of multiple mines within a single catchment and provide evidence that mines reclaimed nearly two decades ago continue to contribute significantly to water quality degradation within this watershed.